KR20140002543A - Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus - Google Patents

Abstract

An electrophotographic photosensitive body of the present invention includes a supporter, an undercoating layer formed on the supporter, and a photosensitive layer formed on the undercoating layer. The undercoating layer has a structure represented by chemical formula C1 or C2. In the chemical formula C1 and C2, R11-R16 and R22-R25 are hydrogen atoms, methylene groups, monovalent groups represented by -CH2OR2, groups represented by chemical formula i, and groups represented by chemical formula ii.

Description

TECHNICAL FIELD [0001] The present invention relates to an electrophotographic photoreceptor, a process cartridge, and an electrophotographic apparatus using the electrophotographic photoreceptor,

The present invention relates to a process cartridge and an electrophotographic apparatus each including an electrophotographic photosensitive member and an electrophotographic photosensitive member.

At present, as an electrophotographic photosensitive member used in a process cartridge and an electrophotographic apparatus, an electrophotographic photosensitive member containing an organic photoconductive material is mainstream. In general, the electrophotographic photosensitive member includes a support and a photosensitive layer formed on the support. An undercoat layer is provided between the support and the photosensitive layer in order to suppress charge injection from the support side to the photosensitive layer side and to suppress the occurrence of image defects such as fog.

In recent years, the thing which has higher sensitivity is used as a charge generating material. However, there is a problem that the charge is likely to stay in the photosensitive layer due to the increased sensitivity of the charge generating material and the ghost is easily generated. Specifically, a phenomenon in which the density increases only in a portion of the output image corresponding to the portion to which light is irradiated at the time of forward rotation, that is, a positive ghost phenomenon is likely to occur.

As a technique for suppressing (reducing) such a ghost phenomenon, a technique of including an electron transporting material in an undercoat layer is known. In order to prevent the electron transport material from eluting during formation of the photosensitive layer on the undercoat layer, when the electron transport material is included in the undercoat layer, the undercoat layer composed of a curable material that is poorly soluble to the solvent of the photosensitive layer coating liquid. Techniques for using are known.

Japanese Patent Publication No. 2009-505156 discloses an undercoat layer containing a condensation polymer (electron transport material) having an aromatic tetracarbonylbisimide skeleton and a crosslinking site, and containing a polymer of a crosslinking agent. Japanese Unexamined Patent Publications No. 2003-330209 and Japanese Unexamined Patent Publication No. 2008-299344 disclose an undercoat layer containing a polymer of an electron transporting material having a non-hydrolyzable polymerizable functional group.

In recent years, electrophotographic images are required to have better image quality, and the allowable range for the positive ghost described above has become very strict.

The present inventors have conducted research to investigate the suppression (reduction) of positive ghosts, in particular, the variation of the level of positive ghosts before and after continuous image output, Japanese Patent Publication No. 2009-505156, Japanese Patent Publication No. 2003-330209 It has been found that there is still room for improvement in the technique disclosed in Japanese Patent Laid-Open No. 2008-299344. In the techniques disclosed in Japanese Patent Laid-Open Publication No. 2009-505156, Japanese Patent Laid-Open Publication No. 2003-330209, and Japanese Patent Laid-Open Publication No. 2008-299344, there are cases where the positive ghost is not sufficiently reduced during the initial stage and repeated use. have.

An aspect of the present invention provides an electrophotographic photosensitive member having a reduced positive ghost and a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.

One disclosed aspect of the present invention includes a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer, wherein the undercoat layer has a structure represented by the following formula (C1), or the following formula (C2) It provides an electrophotographic photosensitive member comprising a structure represented by,

In formulas (C1) and (C2), R ¹¹ to R ¹⁶ and R ²² to R ²⁵ each independently represent a hydrogen atom, a methylene group, a monovalent group represented by -CH ₂ OR ² , and the following formula (i) Or a group represented by the following formula (ii), at least one of R ¹¹ to R ¹⁶ , and at least one of R ²² to R ²⁵ are each a group represented by the following formula (i), and R ^{11 At} least one of R ¹⁶ and at least one of R ²² to R ²⁵ are each a group represented by the following formula (ii), R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ²¹ is An alkyl group, a phenyl group, or the phenyl group substituted by the alkyl group is shown.

In formula (i), R ⁶¹ represents a hydrogen atom or an alkyl group, Y ¹ represents a single bond, an alkylene group or a phenylene group, and D ¹ represents a divalent group represented by any one of the following formulas (D1) to (D4) "*" Represents the side which couple | bonds with the nitrogen atom of the said general formula (C1), or the nitrogen atom of the said general formula (C2),

In formula (ii), D ² represents a divalent group represented by any one of the above formulas (D1) to (D4), and α represents an alkylene group having 1 to 6 atoms in the main chain and an alkyl group having 1 to 6 carbon atoms An alkylene group having 1 to 6 atoms in the main chain substituted with an alkylene group, an alkylene group having 1 to 6 atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or a phenyl group An alkylene group having 1 to 6 atoms in the main chain substituted by 1, wherein one of the carbon atoms in the main chain of the alkylene group may be substituted by O, S, NH or NR ¹ , and R ¹ has 1 to 1 carbon atoms 6 represents an alkyl group, β represents a phenylene group, a phenylene group substituted by an alkyl group having 1 to 6 carbon atoms, a phenylene group substituted by a nitro group, or a phenylene group substituted by a halogen atom, and γ is won Embroidery represents an alkylene group having 1 to 6 or an alkylene group having 1 to 6 atoms in the main chain substituted by an alkyl group having 1 to 6 carbon atoms, and l, m and n each independently represent 0 or 1, A ¹ represents a divalent group represented by any one of the following formulas (A1) to (A9), and “*” represents a side bonded to the nitrogen atom of formula (C1) or the nitrogen atom of formula (C2). ,

In formulas (A1) to (A9), R ¹⁰¹ to R ¹⁰⁶ , R ²⁰¹ to R ²¹⁰ , R ³⁰¹ to R ³⁰⁸ , R ⁴⁰¹ to R ⁴⁰⁸ , R ⁵⁰¹ to R ⁵¹⁰ , R ⁶⁰¹ to R ⁶⁰⁶ , R ⁷⁰¹ to R ⁷⁰⁸ , R ⁸⁰¹ to R ⁸¹⁰ and R ⁹⁰¹ to R ⁹⁰⁸ each independently represent a single bond, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, a dialkylamino group, a hydroxy group, a substituted or unsubstituted alkyl group , A substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; At least two of R ¹⁰¹ to R ¹⁰⁶ , at least two of R ²⁰¹ to R ²¹⁰ , at least two of R ³⁰¹ to R ³⁰⁸ , at least two of R ⁴⁰¹ to R ⁴⁰⁸ , at least two of R ⁵⁰¹ to R ⁵¹⁰ , At least two of R ⁶⁰¹ to R ⁶⁰⁶ , at least two of R ⁷⁰¹ to R ⁷⁰⁸ , at least two of R ⁸⁰¹ to R ⁸¹⁰ and at least two of R ⁹⁰¹ to R ⁹⁰⁸ are single bonds; The substituent of the substituted alkyl group is an alkyl group, an aryl group, a halogen atom, or a carbonyl group; The substituent of the substituted aryl group or heterocyclic group is a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen substituted alkyl group, an alkoxy group or a carbonyl group; Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ , Z ⁵⁰¹ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom; R ²⁰⁹ and R ²¹⁰ are absent when Z ²⁰¹ is an oxygen atom; R ²¹⁰ is absent when Z ²⁰¹ is a nitrogen atom; R ³⁰⁷ and R ³⁰⁸ are absent when Z ³⁰¹ is an oxygen atom; R ³⁰⁸ is absent when Z ³⁰¹ is a nitrogen atom, and R ⁴⁰⁷ and R ⁴⁰⁸ are absent when Z ⁴⁰¹ is an oxygen atom; When Z ⁴⁰¹ is a nitrogen atom, R ⁴⁰⁸ is not present, when Z is an oxygen atom ⁵⁰¹ R ⁵⁰⁹ and R ⁵¹⁰ is absent, Z ⁵⁰¹ does not exist ⁵¹⁰ R when the nitrogen atom.

Another disclosed aspect of the present invention provides a process cartridge detachably attached to a main body of an electrophotographic apparatus by integrally supporting the above-mentioned electrophotographic photosensitive member and at least one device selected from the group consisting of a charging device, a developing device, a transfer device and a cleaning device. To provide.

Another disclosed aspect of the present invention provides an electrophotographic apparatus including the electrophotographic photosensitive member, charging device, exposure means, developing device, and transfer device.

Aspects of the present invention provide an electrophotographic photosensitive member having a reduced positive ghost, a process cartridge and an electrophotographic apparatus each including the electrophotographic photosensitive member.

Additional features of the present invention will become apparent from the following detailed description of exemplary embodiments with reference to the attached drawings.

1 shows a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photosensitive member.
FIG. 2 is a diagram illustrating an image for ghost evaluation used in ghost image evaluation. FIG.
3 is a diagram illustrating a one dot stair pattern image.
4A and 4B show a layer structure of an electrophotographic photosensitive member according to an aspect of the present invention.

The undercoat layer which concerns on one Embodiment of this invention is a layer (cured layer) which has a structure represented by following General formula (C1), or a structure represented by following General formula (C2).

The present inventors speculate on the reason why the electrophotographic photosensitive member including the undercoat layer according to the embodiment of the present invention has the effect of achieving the reduction of the generation of positive ghost at a high level.

In the electrophotographic photosensitive member according to one embodiment of the present invention, the undercoat layer has a structure represented by formula (C1) or formula (C2) in which a melamine compound or guanamine compound is bonded to both an electron transporting material and a resin. .

In the structure represented by the formula (C1) or (C2), a triazine ring having electron withdrawing properties and an electron transporting site represented by A ¹ are bonded together to interact with each other, thereby being considered as a factor of electron transport properties. It is assumed that the level is formed. By making this conduction level uniform, it is considered that electrons are less likely to be trapped and residual charges are reduced.

However, in the undercoat layer containing such a some component, the component which has the same structure may aggregate easily. In the undercoat layer according to the embodiment of the present invention, the triazine ring bonded to the electron transport site is bonded to the molecular chain of the resin (group represented by the formula (i)), whereby the same component due to aggregation in the undercoat layer By suppressing the ubiquitous of, uniform conduction level is formed. As a result, electrons are less likely to be trapped, residual charges are reduced during long-term repeated use, and it is considered that generation of positive ghost is suppressed. Moreover, since hardened | cured material which has a structure represented by general formula (C1) or (C2) is formed, it is thought that elution of an electron carrying material is suppressed and a ghost reduction effect is provided at a higher level.

An electrophotographic photosensitive member according to an embodiment of the present invention includes a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer. The photosensitive layer may be a photosensitive layer having a stacked structure (functionally separated structure) including a charge generating layer containing a charge generating material and a charge transporting layer containing a charge transporting material. From the viewpoint of electrophotographic characteristics, the photosensitive layer having a laminated structure may be a normal-order-type photosensitive layer laminated in the order of the charge generating layer and the charge transporting layer from the support side.

4A and 4B are diagrams showing an example of a layer structure of an electrophotographic photosensitive member according to one embodiment of the present invention. 4A and 4B, reference numeral 101 is a support, reference numeral 102 is an undercoat layer, reference numeral 103 is a photosensitive layer, reference numeral 104 is a charge generating layer, and reference numeral 105 is a charge transport layer.

As a general electrophotographic photosensitive member, a cylindrical electrophotographic photosensitive member including a photosensitive layer (charge generating layer, charge transport layer) formed on a cylindrical support is widely used. The electrophotographic photosensitive member may have a belt shape and a sheet shape.

(Undercoat layer)

An undercoat layer is provided between the support or the conductive layer described later and the photosensitive layer. The undercoat layer has a structure represented by the following general formula (C1) or a structure represented by the following general formula (C2). In other words, the undercoat layer contains a cured product (polymer) having a structure represented by the following formula (C1) or a structure represented by the following formula (C2):

In formula (C1), R ¹¹ to R ¹⁶ and R ²² to R ²⁵ each independently represent a hydrogen atom, a methylene group, a monovalent group represented by -CH ₂ OR ² , a group represented by the following formula (i), Or a group represented by the following formula (ii); ^At least one of R ¹¹ to R ¹⁶ and at least one of R ²² to R ²⁵ are each a group represented by the following formula (i); ^At least one of R ¹¹ to R ¹⁶ and at least one of R ²² to R ²⁵ are each a group represented by the following formula (ii); R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; R ²¹ represents an alkyl group, a phenyl group, or a phenyl group substituted by an alkyl group,

In formula (i), R ⁶¹ represents a hydrogen atom or an alkyl group, Y ¹ represents a single bond, an alkylene group or a phenylene group, and D ¹ represents a divalent group represented by any one of the following formulas (D1) to (D4) Wherein the alkyl group may be a methyl group or an ethyl group, the alkylene group may be a methylene group, and “*” in Formula (i) is bonded to a nitrogen atom of Formula (C1), or a nitrogen atom of Formula (C2) Side.

In formula (ii), D ² represents a divalent group represented by any one of the above formulas (D1) to (D4), and α represents an alkylene group having 1 to 6 atoms in the main chain and an alkyl group having 1 to 6 carbon atoms An alkylene group having 1 to 6 atoms in the main chain substituted with an alkylene group, an alkylene group having 1 to 6 atoms in the main chain substituted with a benzyl group, an alkylene group having 1 to 6 atoms in the main chain substituted with an alkoxycarbonyl group, or a phenyl group An alkylene group having 1 to 6 atoms in the main chain substituted by 1, wherein one of the carbon atoms in the main chain of the alkylene group may be substituted by O, S, NH or NR ¹ , and R ¹ has 1 to 1 carbon atoms 6 represents an alkyl group, β represents a phenylene group, a phenylene group substituted by an alkyl group having 1 to 6 carbon atoms, a phenylene group substituted by a nitro group, or a phenylene group substituted by a halogen atom, and γ is won Embroidery represents an alkylene group having 1 to 6 or an alkylene group having 1 to 6 atoms in the main chain substituted by an alkyl group having 1 to 6 carbon atoms, and l, m and n each independently represent 0 or 1, A ¹ represents a divalent group represented by any one of the following formulas (A1) to (A9), wherein “*” in the formula (ii) represents a nitrogen atom of the formula (C1) or a nitrogen atom of the formula (C2) Represents the side that binds to,

In formulas (A1) to (A9), R ¹⁰¹ to R ¹⁰⁶ , R ²⁰¹ to R ²¹⁰ , R ³⁰¹ to R ³⁰⁸ , R ⁴⁰¹ to R ⁴⁰⁸ , R ⁵⁰¹ to R ⁵¹⁰ , R ⁶⁰¹ to R ⁶⁰⁶ , R ⁷⁰¹ to R ⁷⁰⁸ , R ⁸⁰¹ to R ⁸¹⁰ and R ⁹⁰¹ to R ⁹⁰⁸ each independently represent a single bond, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, a dialkylamino group, a hydroxy group, a substituted or unsubstituted alkyl group , A substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; At least two of R ¹⁰¹ to R ¹⁰⁶ , at least two of R ²⁰¹ to R ²¹⁰ , at least two of R ³⁰¹ to R ³⁰⁸ , at least two of R ⁴⁰¹ to R ⁴⁰⁸ , at least two of R ⁵⁰¹ to R ⁵¹⁰ , At least two of R ⁶⁰¹ to R ⁶⁰⁶ , at least two of R ⁷⁰¹ to R ⁷⁰⁸ , at least two of R ⁸⁰¹ to R ⁸¹⁰ and at least two of R ⁹⁰¹ to R ⁹⁰⁸ are single bonds; Substituent of the substituted alkyl group is an alkyl group, an aryl group, a halogen atom, or a carbonyl group; The substituent of the substituted aryl group or heterocyclic group is a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen substituted alkyl group, an alkoxy group or a carbonyl group; Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ , Z ⁵⁰¹ each independently represents a carbon atom, a nitrogen atom, or an oxygen atom, and when R ²⁰¹ is an oxygen atom, R ²⁰⁹ and R ²¹⁰ are not present; R ²¹⁰ is absent when Z ²⁰¹ is a nitrogen atom; R ³⁰⁷ and R ³⁰⁸ are absent when Z ³⁰¹ is an oxygen atom; When Z ³⁰¹ is a nitrogen atom R ³⁰⁸ is absent; R ⁴⁰⁷ and R ⁴⁰⁸ are absent when Z ⁴⁰¹ is an oxygen atom; If Z ⁴⁰¹ is a nitrogen atom R ⁴⁰⁸ is absent; R ⁵⁰⁹ and R ⁵¹⁰ are absent when Z ⁵⁰¹ is an oxygen atom; R ⁵¹⁰ is absent when Z ⁵⁰¹ is a nitrogen atom.

The structure represented by the formula (C1) includes a site derived from the melamine compound. The structure represented by the formula (C2) includes a site derived from a guanamine compound. The site derived from the melamine compound, or the site derived from the guanamine compound, is combined with the group represented by the formula (i) and the group represented by the formula (ii). The group represented by the formula (i) is a site derived from the resin. The group represented by formula (ii) is an electron transport site represented by any one of formulas (A1) to (A9) in formula (ii).

Each of the structure represented by the formula (C1) and the structure represented by the formula (C2) is bonded to at least one group represented by the formula (i) and at least one group represented by the formula (ii). The remaining group not bonded to the group represented by the formula (i) or the group represented by the formula (ii) is a hydrogen atom, a methylene group, or a monovalent group represented by -CH ₂ OR ² (R ² is a hydrogen atom or a carbon atom To an alkyl group of 1 to 10). When the remaining group represents a methylene group, the structure may be bonded to the melamine structure or guanamine structure through the methylene group.

In the general formula (ii), the number of atoms of the main chain other than A ¹ is preferably 12 or less and more preferably 2 or more and 9 or less, since the distance between the triazine ring and the electron transporting site is appropriate, and therefore, due to interaction Smooth electron transport is provided, further reducing positive ghosts.

In formula (ii), β may represent a phenylene group. α may represent an alkylene group having 1 to 5 atoms in the main chain substituted by an alkyl group having 1 to 4 carbon atoms, or may represent an alkylene group having 1 to 5 atoms in the main chain.

The structure represented by the said general formula (C1) in the undercoat layer, or the structure represented by the said general formula (C2) may be 30 mass% or more and 100 mass% or less with respect to the total mass of an undercoat layer.

The content of the structure represented by the formula (C1) or (C2) in the undercoat layer can be analyzed by a general analysis method. An example of an analysis method is shown below. The content of the structure represented by the formula (C1) or (C2) is determined by Fourier transform infrared spectroscopy (FT-IR) using the KBr-tablet method. By using a sample having a different amount of melamine added to the KBr powder, a calibration curve is prepared based on the absorption caused by the triazine ring, so that the content of the structure represented by the formula (C1) or (C2) in the undercoat layer can be calculated.

In addition, the structure represented by general formula (C1) or (C2) is a measuring method, such as solid ¹³ C-NMR measurement, mass spectrometry measurement, MS spectrum measurement by pyrolysis GC-MS analysis, characteristic absorption measurement by infrared spectroscopic analysis, etc. This can be confirmed by analyzing the undercoat layer. For example, solid ¹³ C-NMR measurement using CMX-300 Infiniy manufactured by Chemagnetics, observation nucleus: ¹³ C, reference substance: polydimethylsiloxane, integration count: 8192, pulse sequence: CP / MAS, DD / MAS , Pulse width: 2.1 µsec (DD / MAS), 4.2 µsec (CP / MAS), contact time: 2.0 msec, sample rotational speed: 10 Hz.

For mass spectrometry, using a mass spectrometer (MALDI-TOF MS, model: ultraflex from Burker Daltonics, Inc.), acceleration voltage: 20 kV, mode: Reflector, molecular weight standard: molecular weight under conditions of fullerene C ₆₀ Was measured. The molecular weight was determined based on the peak maximum observed.

The molecular weight of the resin was measured by gel permeation chromatography "HLC-8120" manufactured by Toso Corporation, and calculated in terms of polystyrene.

In addition to the structure represented by the general formula (C1) or (C2), the undercoat layer may be, for example, organic particles, inorganic particles, metal oxide particles, leveling agents, It may contain a catalyst for promoting hardening. However, it is preferable that they are less than 50 mass% with respect to the total mass of an undercoat layer, and it is more preferable that they are less than 20 mass%. The film thickness of the undercoat layer may be 0.1 µm or more and 5.0 µm or less.

Although the specific example of the structure represented by the said general formula (C1) or (C2) is shown below, this invention is not limited to these. In each embodiment, the number of atoms of main chains other than A ¹ provided as an electron transport site is described. In Tables 1 to 27, the binding sites are indicated by dashed lines. The term "single" refers to a single bond. The left and right directions of the group represented by the formula (i) and the group represented by the formula (ii) and the left and right directions of the respective structures shown in Tables 1 to 27 are the same.

The undercoating layer having a structure represented by the above formula (C1) or a structure represented by the above formula (C2) is a melamine compound or guanamine compound, a resin having a polymerizable functional group capable of reacting with these compounds, and a compound thereof. It is formed by apply | coating the undercoat layer coating liquid containing the electron carrying material which has a polymeric functional group, forming a coating film, and thermosetting the obtained coating film.

(Melamine compound, guanamine compound)

Melamine compound and guanamine compound are demonstrated. The melamine compound or guanamine compound is synthesized by a known method using, for example, melamine or guanamine and formaldehyde.

Below, the specific example of a melamine compound and a guanamine compound is demonstrated. The embodiments described below are monomers, but oligomers (multimers) of the monomers may be contained. From the viewpoint of suppression of positive ghost, the monomer may be contained in an amount of 10% by mass or more based on the total mass of the monomer and the multimer. The degree of polymerization of the multimer may be 2 or more and 100 or less. The multimer and monomer may be used by mixing two or more kinds. Generally available melamine compounds are, for example, SUPER MELAMI No. 90 (manufactured by Nippon Yushi Co., Ltd.); SUPER BECKAMIN (R) TD-139-60, L-105-60, L127-60, L110-60, J-820-60, G-821-60 (manufactured by DIC Corporation); UBAN 2020 (manufactured by Mitsui Chemicals); SUMITEX RESIN M-3 (manufactured by Sumitomo Kagaku Corporation); NIKALACK MW-30, MW-390, MX-750LM (made by Nippon Carbide High School) is mentioned. Generally available guanamine compounds include, for example, SUPER BECKAMIN (R) L-148-55, 13-535, L-145-60, TD-126 (manufactured by DIC Corporation); NIKALACK BL-60 and BX-4000 (made by Nippon Carbide) is mentioned.

Below, the specific example of a melamine compound is shown.

Below, the specific example of guanamine compound is shown.

An electron transporting material containing a polymerizable functional group capable of reacting with the melamine compound or guanamine compound will be described. The electron transport material is derived from the structure represented by A ¹ in formula (ii). The electron transporting material may be a monomer containing one electron transporting site represented by one of formulas (A1) to (A9), or may be an oligomer containing a plurality of electron transporting sites. In the case of an oligomer, an oligomer can have a weight average molecular weight (Mw) of 5000 or less from a viewpoint of suppressing an electron trap.

Examples of electron transport materials are described below. Specific examples of the compound having a structure represented by the general formula (A1) will be described below.

The specific example of the compound which has a structure represented by the said General formula (A2) below is shown.

The specific example of the compound which has a structure represented by the said General formula (A3) below is shown.

The specific example of the compound which has a structure represented by the said General formula (A4) below is shown.

The specific example of the compound which has a structure represented by the said General formula (A5) below is shown.

The specific example of a compound represented by the said general formula (A6) below is shown.

The specific example of a compound represented by the said general formula (A7) below is shown.

The specific example of a compound represented by the said general formula (A8) below is shown.

The specific example of a compound represented by the said general formula (A9) below is shown.

Derivatives having a structure represented by the formula (A1) (derivatives of electron transport materials) are described, for example, in US Pat. No. 4,442,193, US Pat. No. 4,992,349, US Pat. No. 5,468,583, Chemistry of materials, Vol. 19, No. 11, pp. 2703-2705 (2007) can be synthesized using a known synthesis method. The said derivative can be synthesize | combined by reaction of a monoamine derivative with naphthalene tetracarboxylic dianhydride which can be purchased from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc.

The compound represented by the formula (A1) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group and methoxy group) that can be cured (polymerized) with a melamine compound or guanamine compound. As a method of introducing these polymerizable functional groups into the derivative which has a structure represented by general formula (A1), the method of introduce | transducing a polymeric functional group directly; There exists a method of introducing the structure which has a functional group used as a precursor of the said polymerizable functional group or a polymerizable functional group. As the latter method, for example, a method of introducing a functional group-containing aryl group into a halogenated compound of a naphthylimide derivative by a cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group. As a raw material for synthesizing a naphthylimide derivative, there is a method of using a naphthalene tetracarboxylic dianhydride derivative or a monoamine derivative containing a functional group which can be formed as the polymerizable functional group or a precursor of the polymerizable functional group. .

The derivative which has a structure represented by general formula (A2) can be purchased from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc., for example. Alternatively, the derivative may be derived from a phenanthrene derivative or a phenanthroline derivative, as defined by Chem. Educator No. 6, pp.227-234 (2001), Journal of Organic Synthetic Chemistry, Japan, Vol. 15, pp.29-32 (1957), Journal of Organic Synthetic Chemistry, Japan, Vol. 15, pp.32-34 It may be synthesized by the synthesis method described in (1957). Dicyano methylene group can also be introduce | transduced by reaction with malononitrile.

The compound represented by the formula (A2) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) capable of polymerizing with a melamine compound or guanamine compound. As a method of introducing the polymerizable functional group into the derivative having the structure of formula (A2), a method of directly introducing the polymerizable functional group; There exists a method of introducing the structure which has a functional group used as a precursor of a polymerizable functional group or a polymerizable functional group. As the latter method, for example, a method of introducing a functional group-containing aryl group into a halogenated compound of phenanthrenequinone by a cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

The derivative which has a structure represented by General formula (A3) can be purchased, for example from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc. Alternatively, the derivatives may be derived from phenanthrene derivatives or phenanthroline derivatives. Chem. Soc. It may also be synthesized by the synthesis method described in Jpn., Vol. 65, pp. 1006-1011 (1992). Dicyano methylene group can also be introduce | transduced by reaction with malononitrile.

The compound represented by the formula (A3) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) capable of polymerizing with a melamine compound or guanamine compound. As a method of introducing the polymerizable functional group into the derivative having a structure represented by the formula (A3), a method of directly introducing a polymerizable functional group; There exists a method of introducing the structure which has a functional group used as a precursor of a polymerizable functional group or a polymerizable functional group. As the latter method, for example, a method of introducing a functional group-containing aryl group into a halogenated compound of phenanthrolinequinone by a cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

The derivative which has a structure represented by general formula (A4) can be purchased from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc., for example. Alternatively, from the acenaphthequinone derivatives, the synthesis method described in Tetrahedron Letters, Vol. 43, issue 16, pp. 2991-2994 (2002) or Tetrahedron Letters, Vol. 44, issue 10, pp. 2087-2091 (2003). It may be synthesized by. Dicyano methylene group can also be introduce | transduced by reaction with malononitrile.

The compound represented by the formula (A4) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) which can be polymerized with melamine compound or guanamine compound. As a method of introducing the polymerizable functional group into the derivative having a structure represented by the formula (A4), a method of directly introducing a polymerizable functional group; There exists a method of introducing the structure which has a functional group used as a precursor of a polymerizable functional group or a polymerizable functional group. As the latter method, for example, a method of introducing a functional group-containing aryl group into a halogenated compound of acenaphthequinone by a cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

The derivative which has a structure represented by general formula (A5) can be purchased from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matthey Japan Inc., for example. Alternatively, it can be synthesized from fluorenone derivatives and malononitrile by the synthesis method described in US Pat. No. 4,562,132. The derivative may also be synthesized from fluorenone derivatives and aniline derivatives by the synthesis methods described in Japanese Patent Application Laid-open No. Hei 5-279582 and Japanese Patent Application Laid-open No. Hei 7-70038.

The compound represented by the formula (A5) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) capable of polymerizing with melamine compound or guanamine compound. As a method of introducing these polymerizable functional groups into the derivative which has a structure represented by general formula (A5), the method of introduce | transducing a polymeric functional group directly; There exists a method of introducing the structure which has a functional group used as a precursor of a polymerizable functional group or a polymerizable functional group. As the latter method, for example, a method of introducing a functional group-containing aryl group into a halogenated compound of fluorenone by a cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

The derivative having the structure represented by the formula (A6) can be synthesized by the synthesis method described in Chemistry Letters, 37 (3), pp. 360-361 (2008) or Japanese Patent Laid-Open No. 9-151157. Alternatively, the derivative may be purchased from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd. or Johnson Matthey Japan Inc.

The compound represented by the formula (A6) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) capable of polymerizing with a melamine compound or guanamine compound. As a method of introducing these polymerizable functional groups into a derivative having a structure represented by the formula (A6), there is a method of introducing a structure having a functional group that becomes a precursor of a polymerizable functional group or a polymerizable functional group to a naphthoquinone derivative. This method includes, for example, a method of introducing a functional group-containing aryl group into a halogenated compound of naphthoquinone by a cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

The derivative having the structure represented by the formula (A7) can be synthesized by the synthesis method described in Japanese Patent Laid-Open No. Hei 1-206349 or PPCI / Japan Hardcopy '98, p. 207 (1998). For example, the said derivative can be synthesize | combined using the phenol derivative which can be purchased from Tokyo Kasei Kogyo Co., Ltd. or Sigma Aldrich Japan Co., Ltd. as a raw material.

The compound represented by the formula (A7) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) capable of polymerizing with a melamine compound or guanamine compound. As a method of introducing these polymerizable functional groups into a derivative having a structure represented by the formula (A7), there is a method of introducing a structure having a functional group that becomes a precursor of a polymerizable functional group or a polymerizable functional group. As this method, For example, the method of introduce | transducing a functional group containing aryl group into the halogenated compound of diphenoquinone by the cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

Derivatives having the structure represented by the formula (A8) can be synthesized using, for example, known synthetic methods described in the Journal of the American Chemical Society, Vol. 129, No. 49, pp. 15259-78 (2007). Can be. For example, the derivative is synthesized by a reaction between perylenetetracarboxylic dianhydride and a monoamine derivative, available from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd. or Johnson Matthey Japan Inc. Can be.

The compound represented by the formula (A8) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) capable of polymerizing with a melamine compound or guanamine compound. As a method of introducing these polymerizable functional groups into the derivative which has a structure represented by general formula (A8), the method of introduce | transducing a polymeric functional group directly; There exists a method of introducing the structure which has a functional group used as a precursor of a polymerizable functional group or a polymerizable functional group. As the latter method, for example, a method in which a cross-coupling reaction of a halogenated compound of a perylene imide derivative with a palladium catalyst and a base is used; There is a method using a cross coupling reaction using a FeCl ₃ catalyst and a base. As a synthetic raw material of a perylene imide derivative, there exists a method of using the perylene tetracarboxylic dianhydride derivative or monoamine derivative containing the said functional group or the functional group used as a precursor of a polymerizable functional group.

The derivative which has a structure represented by general formula (A9) can be purchased from Tokyo Kasei Kogyo Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Johnson Matty Japan Inc., for example.

The compound represented by the formula (A9) contains a polymerizable functional group (hydroxy group, thiol group, amino group, carboxyl group or methoxy group) which can be polymerized with melamine compound or guanamine compound. As a method of introducing the polymerizable functional group into a derivative having the structure represented by the formula (A9), a method of introducing a structure having a functional group which becomes a precursor of a polymerizable functional group or a polymerizable functional group to a commercially available anthraquinone derivative is have. As this method, For example, the method of introduce | transducing a functional group containing aryl group into the halogenated compound of anthraquinone by the cross coupling reaction using a palladium catalyst and a base; A method of introducing a functional group-containing alkyl group by a cross coupling reaction using a FeCl ₃ catalyst and a base; There is a method of reacting an epoxy compound or CO ₂ after a lithium substitution reaction to introduce a hydroxyalkyl group or a carboxyl group.

(Suzy)

Resin containing the polymerizable functional group which can react with a melamine compound or a guanamine compound is demonstrated below. The resin contains a group represented by the formula (i). This resin is obtained by polymerizing the monomer containing a polymerizable functional group (hydroxy group, a thiol group, an amino group, a carboxyl group, or a methoxy group) which can be purchased, for example from Sigma-Aldrich Japan Co., Ltd. and Tokyo Kasei Kogyo Co., Ltd ..

Alternatively, resins are generally available for purchase. As a resin which can be purchased, For example, polyether polyol-type resins, such as Nippon Polyurethane Co., Ltd. make AQD-457, AQD-473, Sanyo Kasei Kogyo Co., Ltd. SANNIX GP-400, GP-700; PHTHALKYD W2343 manufactured by Hitachi Kasei Kogyo Co., Ltd. Watersol S-118 and CD-520 manufactured by DIC Corporation, BECKOLITE M-6402-50 and M-6201-40IM, HARIDIP WH-1188 manufactured by Harima Kasei Co., Ltd., Nippon Yu Polyester polyol resins such as ES3604 and ES6538 manufactured by Picasa; Polyacryl polyol resins such as DIC Corporation, BURNOCK WE-300, and WE-304; Polyvinyl alcohol-based resins such as KURARAY POVAL PVA-203, manufactured by Kuraray Co., Ltd .; Polyvinyl acetal resins such as Sekisui Kagaku Kogyo Co., Ltd. BX-1, BM-1, KS-1, KS-5; Carboxyl group-containing resins such as polyamide-based resin such as Toresin FS-350 manufactured by Nagase Chemtex Co., Ltd., AQUALIC manufactured by Nippon Shokubai Co., Ltd. and FINELEX SG2000 manufactured by Namarishi Co., Ltd .; Polyamine resins such as LUCKAMIDE manufactured by DIC Corporation; And polythiol resins such as Toray Co., Ltd. QE-340M. Among these, polyvinyl acetal resins, polyester polyol resins, and the like are more preferable from the viewpoint of polymerizability and uniformity of the undercoat layer.

It is preferable to exist in the range of 5,000 or more and 400,000 or less, and, as for the weight average molecular weight (Mw) of resin, it is more preferable to exist in the range of 5,000 or more and 300,000 or less.

As a quantification method of the functional group in the resin, for example, titration of a carboxyl group using potassium hydroxide; Titration of amino group using sodium nitrite; Titration of a hydroxyl group using acetic anhydride and potassium hydroxide; Titration of a thiol group using 5,5'-dithiobis (2-nitrobenzoic acid); Calibration curve method using the calibration curve obtained from the IR spectrum of the sample which has a different functional group content is mentioned.

Then, the specific example of resin is shown below.

The ratio of the functional groups contained in the melamine compound and the guanamine compound to the sum of the polymerizable functional groups of the resin and the electron transporting material [the compound having a structure represented by any one of Formulas (A1) to (A9)] is 1: 0.5 to 1 It may be: 3.0 because the proportion of functional groups reacting is high.

As a solvent for preparing the undercoating layer coating liquid, it can be arbitrarily selected from alcohols, aromatic solvents, halogenated hydrocarbons, ketones, ketone alcohols, ethers, esters and the like. Specific examples of solvents that may be used include methanol, ethanol, n-propanol, isopropanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone, cyclohexanone, methyl acetate, acetic acid n- Organic solvents, such as butyl, dioxane, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene, are mentioned. These solvents can be used individually or in mixture of 2 or more types.

Curability of the undercoat layer was confirmed as follows. A coating film of the undercoating layer coating liquid containing a melamine compound or guanamine compound, a resin and an electron transporting material was formed on the aluminum sheet using a Meyer bar. The coating film was heated to dry at 160 ° C. for 40 minutes to form an undercoat layer. The obtained undercoat layer was immersed for 2 minutes in the mixed solvent of cyclohexanone / ethyl acetate (1/1), and it dried at 160 degreeC for 5 minutes. The weight of the undercoat layer before and after dipping was measured. In the present Example, it confirmed that there was no elution of the component of the undercoat layer by immersion (weight difference: within +/- 2%).

(Support)

The support may be a support having conductivity. Supports that can be used include, for example, supports made of metals or alloys such as aluminum, nickel, copper, gold, iron and the like; On insulating bases made of, for example, polyester resins, polycarbonate resins, polyimide resins, or glass, for example of metals of aluminum, silver or gold, or of indium oxide, or of conductive materials, for example of tin oxide And a support on which a thin film is formed.

The surface of the support may be subjected to an electrochemical treatment such as anodization or a wet honing, blasting or cutting process to improve electrical properties and suppress interference fringes.

A conductive layer may be provided between the support and the undercoat layer. The conductive layer is formed by forming a coating film composed of a conductive layer coating liquid on a support, and drying the conductive particles dispersed in the resin. As electroconductive particle, the metal powder consisting of carbon black, acetylene black, aluminum, nickel, iron, nichrome, copper, zinc, silver, and metal oxide powder, such as electroconductive tin oxide and ITO (indium tin oxide), are mentioned, for example. Can be.

Examples of the resin include polyester resins, polycarbonate resins, polyvinyl butyral resins, acrylic resins, silicone resins, epoxy resins, melamine resins, urethane resins, phenol resins and alkyd resins.

As a solvent of a conductive layer coating liquid, an ether solvent, an alcohol solvent, a ketone solvent, and an aromatic hydrocarbon solvent are mentioned, for example. The film thickness of the conductive layer is preferably 0.2 µm or more and 40 µm or less, more preferably 1 µm or more and 35 µm or less, and further preferably 5 µm or more and 30 µm or less.

(Photosensitive layer)

A photosensitive layer is provided on the undercoat layer.

As the charge generating substance, for example, an azo pigment, a perylene pigment, an anthraquinone derivative, an anthrone derivative, a dibenzopyrenquinone derivative, a pyrantrone derivative, a violatron derivative, an isoviolandrone derivative, an indigo derivative, a thioindigo derivative, a metal Phthalocyanine pigments such as phthalocyanine and metal-free phthalocyanine, bisbenzimidazole derivatives, and the like. Among these compounds, azo pigments or phthalocyanine pigments can be used. Among the phthalocyanine pigments, oxytitanium phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine can be used.

When the photosensitive layer is a laminated photosensitive layer, examples of the binder resin used in the charge generating layer include vinyl compounds such as styrene, vinyl acetate, vinyl chloride, acrylate, methacrylate, vinylidene fluoride and trifluoroethylene. Polymers and copolymers; Polyvinyl alcohol resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, polysulfone resin, polyphenylene oxide resin, polyurethane resin, cellulose resin, phenol resin, melamine resin, silicone resin, epoxy resin. . Among these compounds, polyester resins, polycarbonate resins, polyvinyl acetal resins can be used. Polyvinyl acetal can be used.

In the charge generating layer, the ratio of the charge generating material to the binder resin (charge generating material / binder resin) is preferably in the range of 10/1 to 1/10, more preferably in the range of 5/1 to 1/5. Do. Examples of the solvent used for the charge generation layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

The film thickness of the charge generating layer may be 0.05 µm or more and 5 µm or less.

Examples of the hole transporting material include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, benzidine compounds, triarylamine compounds, and triphenylamine, and main or side chain groups derived from these compounds. The polymer which has in is also mentioned.

When the photosensitive layer is a laminated photosensitive layer, as the binder resin used for the charge transport layer (hole transport layer), for example, polyester resin, polycarbonate resin, polymethacrylate resin, polyarylate resin, polysulfone resin, polystyrene resin Can be mentioned. Among them, polycarbonate resins and polyarylate resins can be used. The weight average molecular weight (Mw) of each of the said resins may exist in the range of 10,000 or more and 300,000 or less.

In the charge transport layer, the ratio of the charge transport material and the binder resin (charge transport material / binder resin) is preferably in the range of 10/5 to 5/10, more preferably in the range of 10/8 to 6/10. . The film thickness of the charge transport layer may be 5 µm or more and 40 µm or less. Examples of the solvent used for the charge transport layer coating solution include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents.

Between the support and the undercoat layer or between the undercoat and the photosensitive layer, another layer such as a second undercoat layer containing no polymer according to one embodiment of the present invention may be provided.

On the photosensitive layer (charge transport layer), a protective layer (surface protective layer) containing conductive particles or a charge transport material and a binder resin may be provided. The protective layer may further contain additives such as lubricants. The binder resin of a protective layer can have electroconductivity or charge transport property. In that case, a protective layer may not contain electroconductive particle and charge transport material other than the said resin. The binder resin of the protective layer may be a thermoplastic resin, or may be a curable resin cured by polymerization by heat, light or radiation (for example, an electron beam) or the like.

As a method of forming a layer constituting an electrophotographic photosensitive member such as an undercoat layer, a charge generating layer, a charge transport layer, etc., a coating liquid obtained by dissolving and / or dispersing a material constituting the layer in a solvent is applied, and the resulting coating film is dried and And / or a method of curing to form a layer may be employed. As a method of apply | coating a coating liquid, the immersion coating method (dip coating method), the spray coating method, the curtain coating method, and the spin coating method are mentioned, for example. Among these methods, an immersion coating method can be adopted from the viewpoint of efficiency and productivity.

(Process cartridge and electrophotographic device)

1, the schematic structure of the electrophotographic apparatus containing the process cartridge provided with the electrophotographic photosensitive member is shown.

In FIG. 1, reference numeral 1 denotes a cylindrical electrophotographic photosensitive member which is rotationally driven at a predetermined peripheral speed in the direction indicated by the arrow about the axis 2. The surface (peripheral surface) of the electrophotographic photosensitive member 1 which is rotationally driven is uniformly charged to a positive or negative predetermined potential by the charging device 3 (primary charging device: for example, a charging roller). Then, the exposure light (image exposure light) 4 emitted from the exposure device (not shown) of slit exposure or a laser beam scanning exposure is received, for example. In this way, electrostatic latent images corresponding to desired images are sequentially formed on the surface of the electrophotographic photosensitive member 1.

Thereafter, the electrostatic latent image formed on the surface of the electrophotographic photosensitive member 1 is developed by toner in the developer of the developing device 5 to form a toner image. The toner image formed and held on the surface of the electrophotographic photosensitive member 1 is sequentially placed on the transfer material (for example, paper) P by the transfer bias from the transfer device (for example, the transfer roller) 6. It is transferred. The transfer material P is taken out and fed from the transfer material supply unit (not shown) in synchronization with the rotation of the electrophotographic photosensitive member 1 between the electrophotographic photosensitive member 1 and the transfer device 6 (contact portion).

The transfer material P to which the toner image is transferred is separated from the surface of the electrophotographic photosensitive member 1 and conveyed to the fixing device 8, and the toner image is fixed. Thereafter, the transfer material P is conveyed out of the apparatus as an image forming product (printing or copying).

The surface of the electrophotographic photosensitive member 1 after the transfer of the toner image is cleaned by the cleaning device (for example, the cleaning blade) 7 by removing the remaining developer (toner) after the transfer. The electrophotographic photosensitive member 1 is subjected to antistatic treatment by pre-exposure light (not shown) emitted from a pre-exposure device (not shown), and then repeatedly used for image formation. In addition, as shown in FIG. 1, when the charging device 3 is a contact charging device using a charging roller, for example, full exposure light is not always necessary.

A plurality of components, selected from components such as electrophotographic photosensitive member 1, charging device 3, developing device 5, transfer device 6 and cleaning device 7, are integrally coupled to a process cartridge in a housing Can be configured. The process cartridge may be detachably mounted to, for example, the main body of the electrophotographic apparatus of the copier or the laser beam printer. In Fig. 1, the electrophotographic photosensitive member 1, the charging device 3, the developing device 5, and the cleaning device 7 are integrally supported, and the electrophotographic apparatus main body using a guide member 10 such as a rail. The process cartridge 9 is detachably mounted to the process cartridge 9.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples. Here, the term "part" in an Example represents a "mass part." Now, a synthesis example of the electron transporting material according to the embodiment of the present invention will be described.

(Synthesis Example 1)

First, 5.4 parts of naphthalene tetracarboxylic dianhydride [made by Tokyo Kasei Kogyo Co., Ltd.] and 2-methyl-6-ethyl aniline (made by Tokyo Kasei Kogyo Co., Ltd.) under 200 parts of dimethylacetamides 4 Part and 3-part of 2-amino-1-butanol were added. The mixture was stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the solution was refluxed for 8 hours. The precipitate was separated by filtration and recrystallized with ethyl acetate to obtain 1.0 part of compound (A1-8).

(Synthesis Example 2)

First, 5.4 parts of naphthalene tetracarboxylic dianhydride and 5 parts of 2-aminobutyl acid (Tokyo Kasei Kogyo Co., Ltd.) were added to 200 parts of dimethylacetamides under nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the solution was refluxed for 8 hours. The precipitate was separated by filtration and recrystallized with ethyl acetate to obtain 4.6 parts of compound (A1-42).

(Synthesis Example 3)

First, in 200 parts of dimethylacetamide, under a nitrogen atmosphere, 5.4 parts of naphthalene tetracarboxylic dianhydride, 4.5 parts of 2, 6-diethylaniline (Tokyo Kasei Kogyo Co., Ltd.), 4 parts of 4-2-aminobenzenethiol Added. The mixture was stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the solution was refluxed for 8 hours. The precipitate was separated by filtration and recrystallized with ethyl acetate to obtain 1.3 parts of compound (A1-39).

(Synthesis Example 4)

Chem under a nitrogen atmosphere from 2.8 parts of 4- (hydroxymethyl) phenylboronic acid [manufactured by Sigma Aldrich Japan Co., Ltd.] and phenanthrenequinone [manufactured by Sigma Aldrich Japan Co., Ltd.] to a mixed solvent of 100 parts of toluene and 50 parts of ethanol. . 7.4 parts of 3,6-dibromo-9,10-phenanthrendione synthesize | combined by the synthesis method as described in Educator No. 6, pp.227-234 (2001) were added. 100 parts of 20% sodium carbonate aqueous solution was dripped at the said mixture, and 0.55 part of tetrakis (triphenylphosphine) palladium (0) was added. The resulting mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain 3.2 parts of compound (A2-24).

(Synthesis Example 5)

2.8 parts of 3-aminophenylboric acid monohydrate and phenanthrolinequinone (manufactured by Sigma Aldrich Japan Co., Ltd.) were subjected to 2,7-dibromo-9,10-phenanthrolinequinone in the same manner as in Synthesis Example 4 7.4 parts were synthesized. 7.4 parts of 2,7-dibromo-9,10-phenanthrolinequinone was added to the mixed solvent of 100 parts of toluene and 50 parts of ethanol. 100 parts of 20% sodium carbonate aqueous solution was dripped at the said mixture, and 0.55 part of tetrakis (triphenyl phosphine) palladium (0) was added. The resulting mixture was refluxed for 2 hours. After the reaction, the organic phase was extracted with chloroform, washed with water and dried over anhydrous sodium sulfate. After removing the solvent under reduced pressure, the residue was purified by silica gel chromatography to obtain 2.2 parts of Compound (A3-18).

(Synthesis Example 6)

First, perylene tetracarboxylic dianhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 7.4 parts, 2,6-diethylaniline (manufactured by Tokyo Kasei Kogyo Co., Ltd.) under 200 parts of dimethylacetamide 4 Part and 4-part 2-aminophenylethanol were added. The mixture was stirred at room temperature for 1 hour to prepare a solution. After preparing the solution, the solution was refluxed for 8 hours. The precipitate was separated by filtration and recrystallized with ethyl acetate to obtain 5.0 parts of compound (A8-3).

(Synthesis Example 7)

First, 5.4 parts of naphthalene tetracarboxylic dianhydride and 5.2 parts of leucinol (made by Tokyo Kasei Kogyo Co., Ltd.) were added to 200 parts of dimethylacetamides under nitrogen atmosphere. The mixture was stirred at room temperature for 1 hour and then refluxed for 7 hours. After dimethylacetamide was removed by distillation under reduced pressure, recrystallization was performed with ethyl acetate to obtain 5.0 parts of compound (A1-54).

(Synthesis Example 8)

First, in 200 parts of dimethylacetamide, under nitrogen atmosphere, 5.4 parts of naphthalene tetracarboxylic dianhydride, 2.6 parts of rucinol, 2- (2-aminoethylthio) ethanol [made by Wako Pure Chemical Industries, Ltd.] 2.7 parts Added. The mixture was stirred at room temperature for 1 hour and then refluxed for 7 hours. The obtained product was removed from the black brown solution by distillation under reduced pressure, and then dissolved in an ethyl acetate / toluene mixed solution. After separation by silica gel column chromatography (eluent: ethyl acetate / toluene), the fraction containing the target product was concentrated. The obtained crystals were recrystallized with a toluene / hexane mixed solution to obtain 2.5 parts of compound (A1-55). The production and evaluation of the electrophotographic photosensitive member will be described below.

(Example 1)

An aluminum cylinder (JIS-A3003, aluminum alloy) having a length of 260.5 mm and a diameter of 30 mm was used as a support (conductive support).

Next, 50 parts of titanium oxide particles (powder resistivity: 120 Ω · cm, tin oxide coverage: 40%) coated with oxygen-depleted tin oxide were coated with phenol resin [plyofene J-325, Dainippon Ink Kagaku Kogyo Co., Ltd. Co., Ltd., resin solid content: 60%] 40 parts and 50 parts of methoxypropanol as a solvent (dispersion medium) are put into the sand mill using the glass beads of diameter 1mm, the said mixture is disperse-processed for 3 hours, and a conductive layer coating liquid (Dispersion liquid) was prepared. This conductive layer coating liquid was immersed and applied onto a support. The obtained coating film was dried and thermosetted at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 28 μm.

The average particle size of the titanium oxide particles coated with the oxygen-depleted tin oxide in the conductive layer coating liquid was obtained by using tetrahydrofuran as a dispersion medium using a particle size distribution analyzer (trade name: CAPA700) manufactured by Horiba Limited. By centrifugal sedimentation method, it measured at 5000 rpm and it turned out that it becomes 0.31 micrometer.

Next, 5 parts of compound (A1-8), 3.5 parts of melamine compound (C1-3), 3.4 parts of resin (B1), 0.1 part of dodecylbenzenesulfonic acid provided as a catalyst, 100 parts of dimethylacetimide and 100 parts of methyl ethyl ketone It melt | dissolved in the negative mixed solvent and prepared the undercoat layer coating liquid.

This undercoat layer coating liquid was immersed and applied on the conductive layer. The obtained coating film was hardened (polymerized) by heating at 160 degreeC for 40 minutes, and the undercoat layer whose film thickness is 0.5 micrometer was formed. Table 29 shows structures confirmed by solid ¹³ C-NMR measurement, mass spectrometry measurement, MS spectrum measurement by pyrolysis GC-MS analysis, and characteristic absorption measurement by infrared spectroscopy.

Next, crystal forms exhibiting strong peaks at 7.5 °, 9.9 °, 12.5 °, 16.3 °, 18.6 °, 25.1 ° and 28.3 ° of the Bragg angle (2θ ± 0.2 °) in X-ray diffraction with CuKα characteristic radiation. 10 parts of hydroxygallium phthalocyanine crystals (charge generating substance), 5 parts of polyvinyl butyral resin [brand name: S-LEC BX-1, Sekisui Kagaku Kogyo Co., Ltd. product] and 250 parts of cyclohexanone, diameter 1mm It was put into the sand mill using the glass beads of, and was dispersed for 1.5 hours. Next, the charge generating layer coating liquid was prepared by adding 250 parts of ethyl acetate to this.

The charge generating layer coating liquid was immersed and applied on the undercoat layer. The resulting coating film was dried at 100 ° C. for 10 minutes to form a charge generating layer having a film thickness of 0.18 μm.

Next, 8 parts of the amine compound (hole transport material) represented by the following structural formula 15, the repeating structural unit represented by the following general formula (16-1), and the repeating structural unit represented by the following general formula (16-2) are 5/5 The charge transport layer coating liquid was prepared by dissolving 10 parts of polyarylate resins which have a ratio and the weight average molecular weight (Mw) is 100,000 in the mixed solvent of 40 parts of dimethoxymethane and 60 parts of o-xylene. The charge transport layer coating liquid was immersed and applied onto the charge generating layer. The obtained coating film was dried at 120 ° C. for 40 minutes to form a charge transport layer (hole transport layer) having a film thickness of 15 μm.

In this way, an electrophotographic photosensitive member having a conductive layer, an undercoating layer, a charge generating layer, and a charge transporting layer was prepared on a support.

(evaluation)

The manufactured electrophotographic photosensitive member was subjected to a remodeling printer (primary charging: roller contact DC charging, process speed (120) of Canon's laser beam printer (trade name: LBP-2510) under an environment of 23 ° C. and 50% RH). Mm / sec, laser exposure) The output image was evaluated.

(Positive ghost evaluation)

The cyan process cartridge of the laser beam printer was modified. A potential probe (model: 6000B-8, manufactured by Track Japan Co., Ltd.) was installed at the developing position. The electric potential of the center part of the electrophotographic photosensitive member was measured using a surface electrometer (Model: 344, manufactured by Track Japan Co., Ltd.). In addition, the amount of light used for exposing the image was set so that the dark portion potential Vd was -500V and the light potential potential Vl was -150V.

The manufactured electrophotographic photosensitive member was attached to the cyan process cartridge of the laser beam printer. The resulting process cartridge was mounted in a station of cyan process cartridge. And an image was output.

First, image output was performed continuously in order of one solid white image, five images for ghost evaluation, one solid black image, and five images for ghost evaluation.

Next, a full-color image (character image of 1% of each color printing rate) was output to 5,000 sheets of A4 size plain paper. Then, image output was performed continuously in order of one solid white image, five images for ghost evaluation, one solid black image, and five images for ghost evaluation.

As shown in FIG. 2, the ghost evaluation image is a halftone image of the one dot stair pattern shown in FIG. 3 after a solid square image is output to a white image of the tip portion of the sheet. In Fig. 2, the portion indicated as "ghost" is a portion where ghosts due to a solid image can appear.

The positive ghost was evaluated by measuring the difference in the image density between the halftone image and the ghost portion of the one dot stair pattern. In the spectrophotometer [brand name: X-Rite 504/508, the product made by X-Rite Co., Ltd.], it measured at 10 points of image density differences in one image for ghost evaluation. This operation was performed to all 10 images for ghost evaluation, and the average of 100 points in total was computed. The Macbeth density difference (initial stage) at the time of initial image output was evaluated. Next, the difference (change amount) between the Macbeth density difference after 5,000 sheets of output and the Macbeth density difference at the time of initial image output was calculated, and the variation amount of Macbeth density difference was calculated | required. The smaller the Macbeth concentration difference, the better the suppression of positive ghost. The smaller the difference between the Macbeth density difference after 5,000 sheets of output and the Macbeth density difference at the time of initial image output, the smaller the variation of the positive ghost. The results are shown in Table 29.

(Examples 2 to 115)

The electrophotographic photosensitive member was produced like Example 1 except having changed the kind and content of an electron transport material, resin (resin B), a melamine compound, and a guanamine compound as shown in Tables 29-31. Similarly, positive ghosts were evaluated. The results are shown in Tables 29-31.

(Example 116)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the preparation of the conductive layer coating liquid, the undercoat layer coating liquid, and the charge transport layer coating liquid was changed as follows. Similarly, positive ghosts were evaluated. The results are shown in Table 31.

Preparation of the conductive layer coating liquid was changed as follows. First, 214 parts of titanium oxide (TiO ₂ ) particles coated with oxygen-depleted tin oxide (SnO ₂ ) provided as metal oxide particles, 132 parts of phenol resin (trade name: Plyofene J-325) provided as a binder resin, and 98 parts of 1-methoxy-2-propanol provided as a solvent were put into the sand mill using 450 parts of glass beads of 0.8 mm in diameter. Dispersion was performed on the conditions which show rotation speed 2000rpm, dispersion processing time 4.5 hours, and the preset temperature of cooling water 18 degreeC, and the dispersion liquid was obtained. Glass beads were removed from the dispersion by a mesh (scale: 150 µm).

Silicone resin particles provided as a surface roughness imparting material so as to be 10 mass% with respect to the total mass of the metal oxide particles and the binder resin in the dispersion after removing the glass beads [trade name: Tospearl 120, manufactured by Momentive Performance Materials Co., Ltd. , Average particle size: 2 μm] was added to the dispersion. Moreover, the silicone oil (brand name: SH28PA, Dow Corning Toray Co., Ltd. product) provided as a leveling agent was added to the dispersion liquid so that it may become 0.01 mass% with respect to the total mass of the metal oxide particle and binder resin in a dispersion liquid. The conductive layer coating liquid was prepared by stirring the obtained mixture. This conductive layer coating liquid was immersed and applied onto a support. The obtained coating film was dried and thermosetted at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 30 μm.

The preparation of the undercoat coating liquid was changed as follows. First, 5 parts of compound (A1-54), 3.5 parts of melamine compound (C1-3), 3.4 parts of resin (B25), 0.1 part of dodecylbenzenesulfonic acid provided as a catalyst, 100 parts of dimethylacetamide and 100 parts of methyl ethyl ketone It melt | dissolved in the mixed solvent and prepared the undercoat layer coating liquid. This undercoat layer coating liquid was immersed and applied on the conductive layer. The obtained coating film was cured (polymerized) by heating at 160 ° C. for 40 minutes to form an undercoat layer having a thickness of 0.5 μm. Table 31 shows the structure confirmed by solid ¹³ C-NMR measurement, mass spectrometry measurement, MS spectrum measurement by pyrolysis GC-MS analysis, and characteristic absorption measurement by infrared spectroscopic analysis.

The preparation of the charge transport layer coating liquid was changed as follows. Firstly, 9 parts of a charge transport material having a structure represented by the above formula (15), 1 part of a charge transport material having a structure represented by the following formula (18), a repeating structural unit represented by the following formula (24) as a resin, 3 parts of polyester resin F (weight average molecular weight: 90,000) which have a repeating structural unit represented by following formula (26) and a repeating structural unit represented by following formula (25) in 7: 3 ratio, and following formula (27) 7 parts of polyester resin H (weight average molecular weight: 120,000) containing the repeating structural unit represented by the following formula and the repeating structural unit represented by following General formula (28) in 5: 5 ratio: 30 parts of dimethoxymethane, and o-xylene The charge transport layer coating liquid was prepared by dissolving in 50 parts of mixed solvents. In the polyester resin F, content of the repeating structural unit represented by following formula (24) was 10 mass%, and content of the repeating structural unit represented by following formula (25) and formula (26) was 90 mass%.

The charge transport layer coating liquid was immersed and applied onto the charge generating layer and dried at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 16 μm. It was confirmed that the obtained charge transport layer had a domain structure in which the polyester resin F was contained in the matrix containing the charge transport material and the polyester resin H.

(Example 117)

An electrophotographic photosensitive member was produced in the same manner as in Example 116 except that the preparation of the charge transport layer coating liquid was changed as follows. Similarly, positive ghosts were evaluated. The results are shown in Table 31.

The preparation of the charge transport layer coating liquid was changed as follows. First, 9 parts of charge transport materials having a structure represented by the formula (15), 1 part of charge transport materials having a structure represented by the formula (18), and a resin having a repeating structure represented by the following formula (29) 10 parts of polycarbonate resin I (weight average molecular weight: 70,000) and the repeating structural unit represented by following formula (29), the repeating structural unit represented by following formula (30), and the following formula (31) located in any one of the terminal (31) The charge transport layer coating liquid was prepared by melt | dissolving 0.3 part of polycarbonate resin J (weight average molecular weight: 40,000) which has a structure represented by) in 30 parts of dimethoxymethane and 50 parts of o-xylene mixed solvents. In polycarbonate resin J, the total mass of the repeating structural unit represented by the following general formula (30) or (31) was 30 mass%. The charge transport layer coating solution was immersed and applied onto the charge generating layer, and dried at 120 ° C. for 1 hour to form a charge transport layer having a film thickness of 16 μm.

(Example 118)

An electrophotographic photosensitive member was produced in the same manner as in Example 117 except that 10 parts of polyester resin H (weight average molecular weight: 120,000) were used instead of 10 parts of polycarbonate resin I (weight average molecular weight: 70,000). Similarly, positive ghosts were evaluated. The results are shown in Table 31.

(Examples 119 to 121)

An electrophotographic photosensitive member was produced in the same manner as in Examples 116 to 118 except that the preparation of the conductive layer coating liquid was changed as follows. Similarly, positive ghosts were evaluated. The results are shown in Table 31.

First, 207 parts of titanium oxide (TiO ₂ ) particles coated with tin oxide (SnO ₂ ) doped with phosphorus (P), which is provided as a metal oxide particle, and a phenol resin provided as a binder resin (trade name: plyopenf J- 325) 144 parts and 98 parts of 1-methoxy-2-propanol provided as a solvent were put into the sand mill using 450 parts of 0.8 mm glass beads. The mixture was subjected to dispersion treatment under conditions including a rotational speed of 2000 rpm, a dispersion treatment time of 4.5 hours, and a preset temperature of 18 ° C of cooling water to obtain a dispersion. Glass beads were removed from the dispersion by a mesh (scale: 150 µm).

Silicone resin particles (brand name: Tospearl 120) provided as a surface roughness imparting material were added to the dispersion so as to be 15% by mass relative to the total mass of the metal oxide particles and the binder resin in the dispersion after removing the glass beads. Moreover, the silicone oil (brand name: SH28PA) provided as a leveling agent was added to the dispersion liquid so that it may become 0.01 mass% with respect to the total mass of the metal oxide particle and binder resin in a dispersion liquid. The conductive layer coating liquid was prepared by stirring the said mixture. This conductive layer coating liquid was immersed and applied onto a support. The obtained coating film was dried and thermosetted at 150 ° C. for 30 minutes to form a conductive layer having a film thickness of 30 μm.

(Examples 122 and 123)

An electrophotographic photosensitive member was produced in the same manner as in Example 116 except that the kind and content of the electron transporting material were changed as shown in Table 31. Similarly, positive ghosts were evaluated. The results are shown in Table 31.

(Comparative Examples 1 to 5)

An electrophotographic photosensitive member was produced in the same manner as in Example 1 except that the resin was not contained and the kind and content of the electron transporting substance, the melamine compound, and the guanamine compound were changed as shown in Table 32. Similarly, positive ghosts were evaluated. The results are shown in Table 32.

(Comparative Examples 6 to 10)

The electron transport material was changed to the compound represented by the following general formula (Y-1), and the electrons were changed in the same manner as in Example 1 except that the kind and content of the melamine compound, the guanamine compound and the resin were changed as shown in Table 32. Photosensitive photoreceptors were prepared. Similarly, positive ghosts were evaluated. The results are shown in Table 32.

(Comparative Example 11)

The same procedure as in Example 1 was carried out except that the undercoating layer was formed from a block copolymer (copolymer described in JP-A-2009-505156), a block isocyanate compound and a vinyl chloride-vinyl acetate copolymer represented by the following structural formula. Photosensitive photoreceptors were prepared. Evaluation was performed. The initial stage of the Macbeth concentration was 0.048 and the change in Macbeth concentration was 0.065.

By comparison of Examples and Comparative Examples 1 to 5, Japanese Patent Laid-Open No. 2003-330209 and Japanese Patent Laid-Open No. 2 are compared with an electrophotographic photosensitive member including an undercoat layer having a specific structure according to one embodiment of the present invention. In the structure described in 2008-299344, it turns out that the effect high enough for reduction of the fluctuation | variation of the positive ghost at the time of repeated use may not be acquired. Since resin does not exist, it is considered that the triazine ring and the electron transporting material in the undercoat layer are unevenly distributed, and electrons are likely to stay due to repeated use. By comparison between Example 11 and Comparative Example 11, it can be seen that even in the configuration described in Japanese Patent Publication No. 2009-505156, a sufficiently high effect may not be obtained to reduce the variation of positive ghost at the time of repeated use. . By comparison between Examples and Comparative Examples 6 to 10, in a state where the resin and the electron transporting material are not bonded together and dissolved in a solvent and then dispersed, the reduction of the variation of the positive ghost during initial positive ghost and repeated use It turned out that sufficient effect is not acquired. This is considered to be because the effect of reducing the positive ghost by the combination with the triazine ring is not obtained. When forming the charge generating layer on the undercoat layer, since the electron transporting material moved to the upper layer (charge generating layer), the electron transporting material in the undercoating layer is reduced, and the electron transporting material is mixed in the upper layer, so that the electrons stay. I think it is because.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The following claims are to be accorded the broadest interpretation so as to encompass all such modifications, equivalent structures and functions.

Claims (8)

An electrophotographic photosensitive member comprising a support, an undercoat layer formed on the support, and a photosensitive layer formed on the undercoat layer,
The undercoat layer includes an electrochemical photosensitive member comprising a structure represented by the following general formula (C1) or a structure represented by the following general formula (C2).

[Formula (C1) and (C2),
R ¹¹ to R ¹⁶ and R ²² to R ²⁵ each independently represent a hydrogen atom, a methylene group, a monovalent group represented by -CH ₂ OR ² , a group represented by the following formula (i), or the following formula (ii) Represents a group represented by
^At least one of R ¹¹ to R ¹⁶ and at least one of R ²² to R ²⁵ are each a group represented by the following general formula (i),
^At least one of R ¹¹ to R ¹⁶ and at least one of R ²² to R ²⁵ are each a group represented by the following formula (ii),
R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ²¹ represents an alkyl group, a phenyl group, or a phenyl group substituted by an alkyl group.]

[Formula (i),
R ⁶¹ represents a hydrogen atom or an alkyl group,
Y ¹ represents a single bond, an alkylene group or a phenylene group,
D ¹ represents a divalent group represented by any one of the following general formulas (D1) to (D4),
"*" Represents the side which couple | bonds with the nitrogen atom of the said Formula (C1), or the nitrogen atom of the said Formula (C2)]

[Formula (ii),
D ² represents a divalent group represented by any one of the formulas (D1) to (D4),
α is an alkylene group having 1 to 6 atoms in the main chain, an alkylene group having 1 to 6 atoms in the main chain substituted by an alkyl group having 1 to 6 carbon atoms, or an alkyl having 1 to 6 atoms in the main chain substituted by the benzyl group An alkylene group having 1 to 6 atoms in the main chain substituted by a ethylene group, an alkoxycarbonyl group, or an alkylene group having 1 to 6 atoms in the main chain substituted by a phenyl group,
One of the carbon atoms in the main chain of the alkylene group may be substituted with O, S, NH or NR ¹ , R ¹ represents an alkyl group having 1 to 6 carbon atoms,
β represents a phenylene group, a phenylene group substituted by an alkyl group having 1 to 6 carbon atoms, a phenylene group substituted by a nitro group, or a phenylene group substituted by a halogen atom,
γ represents an alkylene group having 1 to 6 atoms in the main chain or an alkylene group having 1 to 6 atoms in the main chain substituted by an alkyl group having 1 to 6 carbon atoms,
l, m and n are each independently 0 or 1,
A ¹ represents a divalent group represented by any one of the following formulas (A1) to (A9),
"*" Represents the side which couple | bonds with the nitrogen atom of the said Formula (C1), or the nitrogen atom of the said Formula (C2)]

[Formula (A1) to (A9),
R ¹⁰¹ to R ¹⁰⁶ , R ²⁰¹ to R ²¹⁰ , R ³⁰¹ to R ³⁰⁸ , R ⁴⁰¹ to R ⁴⁰⁸ , R ⁵⁰¹ to R ⁵¹⁰ , R ⁶⁰¹ to R ⁶⁰⁶ , R ⁷⁰¹ to R ⁷⁰⁸ , R ⁸⁰¹ to R ⁸¹⁰ and R ⁹⁰¹ To R ⁹⁰⁸ are each independently a single bond, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, a carboxyl group, a dialkylamino group, a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or A substituted or unsubstituted heterocyclic group,
At least two of R ¹⁰¹ to R ¹⁰⁶ , at least two of R ²⁰¹ to R ²¹⁰ , at least two of R ³⁰¹ to R ³⁰⁸ , at least two of R ⁴⁰¹ to R ⁴⁰⁸ , at least two of R ⁵⁰¹ to R ⁵¹⁰ , At least two of R ⁶⁰¹ to R ⁶⁰⁶ , at least two of R ⁷⁰¹ to R ⁷⁰⁸ , at least two of R ⁸⁰¹ to R ⁸¹⁰ and at least two of R ⁹⁰¹ to R ⁹⁰⁸ are single bonds,
The substituent of the substituted alkyl group is an alkyl group, an aryl group, a halogen atom, or a carbonyl group,
The substituent of the substituted aryl group or heterocyclic group is a halogen atom, a nitro group, a cyano group, an alkyl group, a halogen substituted alkyl group, an alkoxy group, or a carbonyl group,
Z ²⁰¹ , Z ³⁰¹ , Z ⁴⁰¹ and Z ⁵⁰¹ each independently represent a carbon atom, a nitrogen atom, or an oxygen atom,
R ²⁰⁹ and R ²¹⁰ are absent when Z ²⁰¹ is an oxygen atom,
R ²¹⁰ is absent when Z ²⁰¹ is a nitrogen atom,
R ³⁰⁷ and R ³⁰⁸ are absent when Z ³⁰¹ is an oxygen atom,
R ³⁰⁸ is absent when Z ³⁰¹ is a nitrogen atom,
R ⁴⁰⁷ and R ⁴⁰⁸ are absent when Z ⁴⁰¹ is an oxygen atom,
R ⁴⁰⁸ is absent when Z ⁴⁰¹ is a nitrogen atom,
R ⁵⁰⁹ and R ⁵¹⁰ are absent when Z ⁵⁰¹ is an oxygen atom,
R ⁵¹⁰ does not exist when Z ⁵⁰¹ is a nitrogen atom] The method of claim 1,
In formula (ii),
α is an alkylene group having 1 to 6 atoms in the main chain, an alkylene group having 1 to 6 atoms in the main chain substituted by an alkyl group having 1 to 6 carbon atoms, or an alkyl having 1 to 6 atoms in the main chain substituted by the benzyl group An alkylene group having 1 to 6 atoms in the main chain substituted by a ethylene group, an alkoxycarbonyl group, or an alkylene group having 1 to 6 atoms in the main chain substituted by a phenyl group,
One of the carbon atoms in the main chain of the alkylene group may be substituted with O, NH or NR ¹ . 3. The method according to claim 1 or 2,
The undercoat layer comprises an electrophotographic photosensitive member comprising a structure represented by the formula (C1) or a cured product having a structure represented by the formula (C2). 3. The method according to claim 1 or 2,
The electrophotographic photosensitive member whose atom number of main chains other than A <^1> of the group represented by the said General formula (ii) is 2-9. 3. The method according to claim 1 or 2,
In formula (ii),
α is an electrophotographic photosensitive member which is an alkylene group having 1 to 5 atoms in the main chain substituted by an alkyl group having 1 to 4 carbon atoms or an alkylene group having 1 to 5 atoms in the main chain. 3. The method according to claim 1 or 2,
In formula (ii),
An electrophotographic photosensitive member wherein β is a phenylene group. A process, in which the electrophotographic photosensitive member according to claim 1 or 2 and one or more devices selected from the group consisting of a charging device, a developing device, a transfer device, and a cleaning device are integrally supported and detachable from the main body of the electrophotographic apparatus. cartridge. An electrophotographic photosensitive member according to claim 1 or 2,
Charging device,
Exposure means,
Developing device,
An electrophotographic device comprising a transfer device.

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